DMAP-Catalyzed Annulation Approach for Modular Assembly of Furan-Fused Chromenes.

With a tandem DMAP-catalyzed reaction between o-AQM, in which it is generated in situ from propargylic amine, and acyl carbene surrogate (from pyridinium ylide), a variety of polyarylated chromenes are assembled in good yields. This process does not require transition-metal catalyst and exhibits easy manipulation of the arene group and good functional group compatibility, particularly the -Br group which can be further transformed to other functionalities by cross-coupling reactions. The modular feature of o-AQM substrates and the simple operation procedures add further advantages to this synthetic method.

Rapid Access of Alkynyl and Alkenyl Coumarins via a Dipyridinium Methylide and Propargylamine Cascade Reaction.

A DMAP-catalyzed cascade approach allowing facile assembly of alkynyl coumarins is reported. By virtue of reactive o-AQM (in situ generated from modular propargylamine) and a new synthetic equivalent of acyl carbene (from pyridinium ylide), the reaction proceeds smoothly to afford a variety of alkynyl coumarins in good-to-excellent yields. This transition-metal-free and oxidant-free process features moderate functional group tolerance, particularly the -Br group; thus, this protocol circumvents the inherent shortcomings of the existing Sonogashira coupling of coumarin triflates. This versatile method is also found to be applicable to the preparation of ß-alkenyl coumarins, resembling the outcomes of the current Heck-type coupling reaction.

A ZnI2-catalyzed regioselective cascade 1,4-conjugate addition/5-exo-dig annulation pathway for one-pot access to heterobiaryl frameworks.

Facile access to π-extended heterobiaryl compounds via a non-cross-coupling strategy has been achieved. In the presence of an inexpensive ZnI2 catalyst and versatile propargylamine and ß-naphthol (or ß-naphthylamine and ß-naphthyl mercaptan) starting materials, a variety of sterically hindered heterobiaryl frameworks can be easily obtained. The present catalytic system offers excellent selectivity, good-to-excellent product yields, and good functional group tolerance including, for instance, -CN, -COOH, -C(O)R, -Br and -Cl groups. This cyclization process is proposed to proceed via in situ generated alkynyl o-quinone methides (o-AQMs), following a cascade intermolecular 1,4-conjugate addition/5-exo-dig annulation/1,3-H shift pathway.

Palladium-Catalyzed N-Arylation of Sulfoximines with Aryl Sulfonates.

Palladium-catalyzed C-N bond coupling reaction between NH-sulfoximines and aryl halides (e.g., -Br, -I, and -Cl and pseudohalides -OTf and -ONf) was successfully achieved. Nevertheless, aryl tosylates/mesylates left much to be achieved. In this report, a general N-arylation of sulfoximines with aryl sulfonates is described. Using Pd(OAc)2/MeO-CM-phos complex, the N-aryl sulfoximine products can be obtained in good-to-excellent yields (up to 99%) with good common functional group compatibility. In addition to arene moieties, alkenyl tosylates are shown to be successful coupling partners.

Palladium-Catalyzed Direct Arylation of Polyfluoroarenes for Accessing Tetra- ortho-Substituted Biaryls: Buchwald-type Ligand Having Complementary -PPh2 Moiety Exhibits Better Efficiency.

The first general examples of direct C-H arylation of electron-deficient polyfluoroarenes with challenging di- ortho-substituted aryl(heteroaryl) chlorides for tetra- ortho-substituted biaryl synthesis are reported. Key to success is the use of Buchwald-type biaryl phosphine ligand, notably with inexpensive -PPh2 moiety (instead of -PCy2 group). Pd(OAc)2 associated with ligand L9 exhibits even higher efficiency than the corresponding SPhos toward this reaction. A wide range of sterically hindered di- ortho-substituted chloroarenes bearing electron-donating or -withdrawing groups are found applicable. Excellent product yields are obtained under mild reaction conditions, and the catalyst loading down to 0.25 mol % of Pd can also be achieved.